Dryer added fabric softening compositions and method of use for the delivery of fragrance derivatives

ABSTRACT

The present invention relates to dryer-activated fabric softening compositions comprising: (A) pro-perfume β-ketoester compounds; (B) fabric softening compounds; and (C) optionally, (1) a carboxylic acid salt of a tertiary amine and/or a tertiary amine ester; and (2) a nonionic softener; wherein, preferably, the Iodine Value of the total number of fatty acyl groups present in (A), (C)(1), and (C)(2) is from about 3 to about 60. These compositions exhibit good antistatic properties as well as improved delivery from a substrate.

This application claims the benefit of priority from Provisional U.S. application Ser. No. 60/034,822, filed Dec. 19, 1996.

TECHNICAL FIELD

The present invention relates to an improvement in dryer activated, e.g., dryer-added, softening products, compositions, and/or the process of making these compositions containing β-ketoester pro-fragrance compounds and methods for accomplishing the delivery of such organic pro-fragrance compounds to textile articles and other surfaces dried with said compositions. These products and/or compositions are either in particulate form, compounded with other materials in solid form, e.g., tablets, pellets, agglomerates, etc., or preferably attached to a substrate. The fragrance is released in fragrance-active form when the dried surface is subsequently contacted with a lower pH environment such as contact with water, carbon dioxide gas, humid air, or the like.

BACKGROUND OF THE INVENTION

Consumer acceptance of laundry products is determined not only by the performance achieved with these products but the aesthetics associated therewith. The perfume systems are therefore an important aspect of the successful formulation of such commercial products.

What perfume system to use for a given product is a matter of careful consideration by skilled perfumers. While a wide array of chemicals and ingredients are available to perfumers, considerations such as availability, cost, and compatibility with other components in the compositions limit the practical options. Thus, there continues to be a need to efficient, low-cost, compatible perfume materials useful for laundry compositions.

Furthermore, due to the high energy input and large air flow in the drying process used in the typical automatic laundry dryers, a large part of most perfumes provided by fabric softener products is lost from the dryer vent. Perfume can be lost even when the fabrics are line dried. The amount of perfume carry-over from a laundry process onto fabrics is often marginal and does not last long on the fabric. Fragrance materials are often very costly and inefficient use in rinse added and dryer added fabric softener compositions and ineffective delivery to fabrics results in a very high cost to both consumers and fabric softener manufacturers. Industry, therefore, continues to look for more efficient and effective fragrance delivery in fabric softener products, especially for improvement in the provision of long-lasting fragrance to the dried fabrics.

BACKGROUND ART

General ester chemistry is described in Carey et al., Advanced Organic Chemistry, Part A, 2nd Ed., pp. 421-426 (Plenum, N.Y.; 1984).

Compositions of fragrance materials (having certain values for Odour Intensity Index, Malodour Reduction Value and Odour Reduction Value) said to be used as fragrance compositions in detergent compositions and fabric conditioning compositions are described in European Patent Application Publication No. 404,470, published Dec. 27, 1990 by Unilever PLC. Example 1 describes a fabric-washing composition containing 0.2% by weight of a fragrance composition which itself contains 4.0% geranyl phenylacetate. A process for scenting fabrics washed with lipase-containing detergents is described in PCT application No. WO 95/04809, published Feb. 16, 1995 by Firmenich S.A.

Esters of perfume alcohols are known in the art for providing extended delivery of fragrances in fabric softening compositions. See, for example, U.S. Pat. No. 5,531,910, Severns, issued Jul. 2, 1996. However, the manufacture of pro-fragrant esters known in the art can present costly and significant synthetic challenges. Derivitization of tertiary fragrance alcohols into simple esters is particularly difficult, often resulting in low yields and increased levels of less desirable side products. Therefore, industry continues to seek improved alternatives for generating pro-fragrances through economic and effective means.

It has now surprisingly been discovered that these problems can unexpectedly be overcome by the use of β-ketoesters as pro-fragrances in dryer added compositions. The hydrophobic β-ketoesters of the present invention demonstrate improved substantivity. These ingredients further provide sustained gradual release of perfume from laundry items over an extended period of time. The use of β-ketoesters also provides an alternative synthetic route to derivatize fragrant alcohols into pro-fragrant compounds. This method is particularly well suited to derivatization of tertiary alcohols. Tertiary alcohols can be derivatized with higher yields and improved purity via this method.

SUMMARY OF THE INVENTION

The present invention relates to dryer-activated fabric softening compositions and articles having improved biodegradability, softness, perfume delivery from sheet substrates (lower m.p. range), and/or antistatic effects, for use in an automatic clothes dryer. These compositions and/or articles comprise, as essential ingredients:

(A) from about 0.01% to about 15%, preferably from about 0.05% to about 10%, more preferably from about 0.1% to about 5% by weight of a β-ketoester of parent perfume alcohol, said β-ketoester having the formula: ##STR1## wherein R, R¹, R², and R³ are described hereinafter (B) from about 10% to about 99.99%, preferably from about 15% to about 90%, more preferably from about 30% to about 85%, and even more preferably from about 30% to about 55%, of fabric softening compound, preferably quaternary ammonium compound, more preferably biodegradable, and even more preferably, selected from the group consisting of the compounds of Formulas I, II, III, IV, and mixtures thereof, as described hereinafter; and

wherein these compositions optionally contain ingredients, as described hereinafter, selected from the group consisting of:

(C) (1) co-softeners which are a carboxylic acid salt of a tertiary amine and/or ester amine;

(2) nonionic softeners;

(3) soil release agents;

(4) cyclodextrin/perfume complexes and free perfume;

(5) stabilizers; and

(6) other minor ingredients conventionally used in textile treatment compositions.

The active fabric softening components preferably contain unsaturation to provide improved antistatic benefits. The Iodine Value of the composition is preferably from about 3 to about 60, more preferably from about 8 to about 50, and even more preferably from about 12 to about 40. The Iodine Value of the composition represents the Iodine Value of the total fatty acyl groups present in components (B), (C)(1), and (C)(2) described below. The unsaturation may be present in one or more of the active components of (B), (C)(1), and/or (C)(2).

DETAILED DESCRIPTION OF THE INVENTION

The compositions of the present invention comprise two essential elements, pro-fragrant β-ketoester ingredients, and ingredients useful for formulating dryer added fabric softening compositions.

A. Pro-fragrant β-Ketoester Ingredients

The compositions of the present invention comprise from about 0.01% to about 15%, preferably from about 0.05% to about 10%, more preferably from about 0.1% to about 5% of pro-fragrant β-keto-ester compounds. β-Keto-esters suitable for use in the present invention have the formula: ##STR2## wherein R is alkoxy derived from a fragrance raw material alcohol. Non-limiting examples of preferred fragrance raw material alcohols include 2,4-dimethyl-3-cyclohexene-1-methanol (Floralol), 2,4-dimethyl cyclohexane methanol (Dihydro floralol), 5,6-dimethyl-1-methylethenylbicyclo[2.2.1]hept-5-ene-2-methanol (Arbozol), α,α,-4-trimethyl-3-cyclohexen-1-methanol (α-terpineol), 2,4,6-trimethyl-3-cyclohexene-1-methanol (Isocyclo geraniol), 4-(1-methylethyl)cyclohexane methanol (Mayol), α-3,3-trimethyl-2-norborane methanol, 1,1-dimethyl-1-(4-methylcyclohex-3-enyl)methanol, 2-phenylethanol, 2-cyclohexyl ethanol, 2-(o-methylphenyl)-ethanol, 2-(m-methylphenyl)ethanol, 2-(p-methylphenyl)ethanol, 6,6-dimethylbicyclo-[3.1.1]hept-2-ene-2-ethanol (nopol), 2-(4-methylphenoxy)-ethanol, 3,3-dimethyl-Δ² -β-norbornane ethanol (patchomint), 2-methyl-2-cyclohexylethanol, 1-(4-isopropylcyclohexyl)-ethanol, 1-phenylethanol, 1,1-dimethyl-2-phenylethanol, 1,1-dimethyl-2-(4-methylphenyl)ethanol, 1-phenylpropanol, 3-phenylpropanol, 2-phenylpropanol (Hydrotropic Alcohol), 2-(cyclododecyl)propan-1-ol (Hydroxy-ambran), 2,2-dimethyl-3-(3-methylphenyl)-propan-1-ol (Majantol), 2-methyl-3-phenylpropanol, 3-phenyl-2-propen-1-ol (cinnamyl alcohol), 2-methyl-3-phenyl-2-propen-1-ol (methylcinnamyl alcohol), α-n-pentyl-3-phenyl-2-propen-1-ol (α-amyl-cinnamyl alcohol), ethyl-3-hydroxy-3-phenyl propionate, 2-(4-methylphenyl)-2-propanol, 3-(4-methylcyclohex-3-ene)butanol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)butanol, 2-ethyl-4-(2,2,3-trimethylcyclopent-3-enyl)-2-buten-1-ol, 3-methyl-2-buten-1-ol (prenol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, ethyl 3-hydroxybutyrate, 4-phenyl-3-buten-2-ol, 2-methyl-4-phenylbutan-2-ol, 4-(4-hydroxyphenyl)butan-2-one, 4-(4-hydroxy-3-methoxyphenyl)butan-2-one, 3-methyl-pentanol, 3-methyl-3-penten-1-ol, 1-(2-propenyl)cyclopentan-1-ol (plinol), 2-methyl-4-phenylpentanol (Pamplefleur), 3-methyl-5-phenylpentanol (Phenoxanol), 2-methyl-5-phenylpentanol, 2-methyl-5-(2,3-dimethyltricyclo[2.2.1.0(2,6)]hept-3-yl)-2-penten-1-ol (santalol), 4-methyl-1-phenyl-2-pentanol, 5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol (sandalore), (1-methyl-bicyclo[2.1.1]hepten-2-yl)-2-methylpent-1-en-3-ol, 3-methyl-1-phenylpentan-3-ol, 1,2-dimethyl-3-(1-methylethenyl)cyclopentan-1-ol, 2-isopropyl-5-methyl-2-hexenol, cis-3-hexen-1-ol, trans-2-hexen-1-ol, 2-isoproenyl-4-methyl-4-hexen-1-ol (Lavandulol), 2-ethyl-2-prenyl-3-hexenol, 1-hydroxymethyl-4-iso-propenyl-1-cyclohexene (Dihydrocuminyl alcohol), 1-methyl-4-isopropenylcyclohex-6-en-2-ol (carvenol), 6-methyl-3-isopropenylcyclohexan-1-ol (dihydrocarveol), 1-methyl-4-isopropenylcyclohexan-3-ol, 4-isopropyl-1-methylcyclohexan-3-ol, 4-tert-butylcyclohexanol, 2-tert-butylcyclohexanol, 2-tert-butyl-4-methylcyclohexanol (rootanol), 4-isopropyl-cyclohexanol, 4-methyl-1-(1-methylethyl)-3-cyclohexen-1-ol, 2-(5,6,6-trimethyl-2-norbornyl)cyclohexanol, isobornylcyclohexanol, 3,3,5-trimethylcyclohexanol, 1-methyl-4-isopropylcyclohexan-3-ol, 1-methyl-4-isopropylcyclohexan-8-ol (dihydroterpineol), 1,2-dimethyl-3-(1-methylethyl)cyclohexan-1-ol, heptanol, 2,4-dimethylheptan-1-ol, 6-heptyl-5-hepten-2-ol (isolinalool), 2,4-dimethyl-2,6-heptandienol, 6,6-dimethyl-2-oxymethyl-bicyclo[3.1.1]hept-2-ene (myrtenol), 4-methyl-2,4-heptadien-1-ol, 3,4,5,6,6-pentamethyl-2-heptanol, 3,6-dimethyl-3-vinyl-5-hepten-2-ol, 6,6-dimethyl-3-hydroxy-2-methylenebicyclo[3.1.1]heptane, 1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol, 2,6-dimethylheptan-2-ol (dimetol), 2,6,6-trimethylbicyclo[1.3.3]heptan-2-ol, octanol, 2-octenol, 2-methyloctan-2-ol, 2-methyl-6-methylene-7-octen-2-ol (myrcenol), 7-methyloctan-1-ol, 3,7-dimethyl-6-octenol, 3,7-dimethyl-7-octenol, 3,7-dimethyl-6-octen-1-ol (citronellol), 3,7-dimethyl-2,6-octadien-1-ol (geraniol), 3,7-dimethyl-2,6-octadien-1-ol (nerol), 3,7-dimethyl-7-methoxyoctan-2-ol (osyrol), 3,7-dimethyl-1,6-octadien-3-ol (linalool), 3,7-dimethyloctan-1-ol (pelagrol), 3,7-dimethyloctan-3-ol (tetrahydrolinalool), 2,4-octadien-1-ol, 3,7-dimethyl-6-octen-3-ol (dihydrolinalool), 2,6-dimethyl-7-octen-2-ol (dihydromyrcenol), 2,6-dimethyl-5,7-octadien-2ol, 4,7-dimethyl-4-vinyl-6-octen-3-ol, 3-methyloctan-3-ol, 2,6-dimethyloctan-2-ol, 2,6-dimethyloctan-3-ol, 3,6-dimethyloctan-3-ol, 2,6-dimethyl-7-octen-2-ol, 2,6-dimethyl-3,5-octadien-2-ol (muguol), 3-methyl-1-octen-3-ol, 7-hydroxy-3,7-dimethyloctanal, 3-nonanol, 2,6-nonadien-1-ol, cis-6-nonen-1-ol, 6,8-dimethylnonan-2-ol, 3-(hydroxymethyl)-2-nonanone, 2-nonen-1-ol, 2,4-nonadien-1-ol, 3,7-dimethyl-1,6-nonadien-3-ol, decanol, 9-decenol, 2-benzyl-M-dioxa-5-ol, 2-decen-1-ol, 2,4-decadien-1-ol, 4-methyl-3-decen-5-ol, 3,7,9-trimethyl-1,6-decadien-3-ol (isobutyl linalool), undecanol, 2-undecen-1-ol, 10-undecen-1-ol, 2-dodecen-1-ol, 2,4-dodecadien-1-ol, 2,7,11-trimethyl-2,6,10-dodecatrien-1-ol (farnesol), 3,7,11-trimethyl-1,6,10,-dodecatrien-3-ol (nerolidol), 3,7,11,15-tetramethylhexadec-2-en-1-ol (phytol), 3,7,11,15-tetramethylhexadec-1-en-3-ol (iso phytol), benzyl alcohol, p-methoxy benzyl alcohol (anisyl alcohol), para-cymen-7-ol (cuminyl alcohol), 4-methyl benzyl alcohol, 3,4-methylenedioxy benzyl alcohol, methyl salicylate, benzyl salicylate, cis-3-hexenyl salicylate, n-pentyl salicylate, 2-phenylethyl salicylate, n-hexyl salicylate, 2-methyl-5-isopropylphenol, 4-ethyl-2-methoxyphenol, 4-allyl-2-methoxyphenol (eugenol), 2-methoxy-4-(1-propenyl)phenol (isoeugenol), 4-allyl-2,6-dimethoxy-phenol, 4-tert-butylphenol, 2-ethoxy-4-methylphenol, 2-methyl-4-vinylphenol, 2-isopropyl-5-methylphenol (thymol), pentyl-ortho-hydroxy benzoate, ethyl 2-hydroxy-benzoate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, 3-hydroxy-5-methoxy-1-methylbenzene, 2-tert-butyl-4-methyl-1-hydroxybenzene, 1-ethoxy-2-hydroxy-4-propenylbenzene, 4-hydroxytoluene, 4-hydroxy-3-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, decahydro-2-naphthol, 2,5,5-trimethyl-octahydro-2-naphthol, 1,3,3-trimethyl-2-norbornanol (fenchol), 3a,4,5,6,7,7a-hexahydro-2,4-dimethyl-4,7-methano-1H-inden-5-ol, 3a,4,5,6,7,7a-hexahydro-3,4-dimethyl-4,7-methano-1H-inden-5-ol, 2-methyl-2-vinyl-5-(1-hydroxy-1-methylethyl)tetra-hydrofuran, β-caryophyllene alcohol, vanillin and mixtures thereof.

A listing of common fragrance raw material alcohols can be found in various reference sources, for example, "Perfume and Flavor Chemicals", Vols. I and II; Steffen Arctander, Allured Pub. Co. (1994) and "Perfumes: Art, Science and Technology"; Muller, P. M. and Lamparsky, D., Blackie Academic and Professional (1994) all of which is incorporated herein by reference.

More preferably, the fragrance raw material alcohol is selected from the group consisting of cis-3-hexen-1-ol, hawthanol [admixture of 2-(o-methylphenyl)-ethanol, 2-(m-methylphenyl)ethanol, and 2-(p-methylphenyl)ethanol], heptan-1-ol, decan-1-ol, 2,4-dimethyl cyclohexane methanol, 4-methylbutan-1-ol, 2,4,6-trimethyl-3-cyclohexene-1-methanol, 4-(1-methylethyl)cyclohexane methanol, 3-(hydroxy-methyl)-2-nonanone, octan-1-ol, 3-phenylpropanol, Rhodinal 70 [3,7-dimethyl-7-octenol, 3,7-dimethyl-6-octenol admixture], 9-decen-1-ol, α-3,3-trimethyl-2-norborane methanol, 3-cyclohexylpropan-1-ol, 4-methyl-1-phenyl-2-pentanol, 3,6-dimethyl-3-vinyl-5-hepten-2-ol, phenyl ethyl methanol; propyl benzyl methanol, 1-methyl-4-isopropenylcyclohexan-3-ol, 4-isopropyl-1-methylcyclohexan-3-ol (menthol), 4-tert-butylcyclohexanol, 2-tert-butyl-4-methylcyclohexanol, 4-isopropylcyclo-hexanol, trans-decahydro-β-naphthol, 2-tert-butylcyclohexanol, 3-phenyl-2-propen-1-ol, 2,7,11-trimethyl-2,6,10-dodecatrien-1-ol, 3,7-dimethyl-2,6-octadien-1-ol (geraniol), 3,7-dimethyl-2,6-octadien-1-ol (nerol), 4-methoxybenzyl alcohol, benzyl alcohol, 4-allyl-2-methoxyphenol, 2-methoxy-4-(1-propenyl)phenol, vanillin, and mixtures thereof.

R¹, R², and R³ are each independently hydrogen, C₁ -C₃₀ substituted or unsubstituted linear alkyl, C₃ -C₃₀ substituted or unsubstituted branched alkyl, C₃ -C₃₀ substituted or unsubstituted cyclic alkyl, C₂ -C₃₀ substituted or unsubstituted linear alkenyl, C₃ -C₃₀ substituted or unsubstituted branched alkenyl, C₃ -C₃₀ substituted or unsubstituted cyclic alkenyl, C₂ -C₃₀ substituted or unsubstituted linear alkynyl, C₃ -C₃₀ substituted or unsubstituted branched alkynyl, C₆ -C₃₀ substituted or unsubstituted alkylenearyl, C₆ -C₃₀ substituted or unsubstituted aryl, C₂ -C₂₀ substituted or unsubstituted alkyleneoxy, C₃ -C₂₀ substituted or unsubstituted alkyleneoxyalkyl, C₇ -C₂₀ substituted or unsubstituted alkylenearyl, C₆ -C₂₀ substituted or unsubstituted alkyleneoxyaryl, and mixtures thereof; provided at least one R¹, R², or R³ is a unit having the formula: ##STR3## wherein R⁴, R⁵, and R⁶ are each independently hydrogen, C₁ -C₃₀ substituted or unsubstituted linear alkyl, C₃ -C₃₀ substituted or unsubstituted branched alkyl, C₃ -C₃₀ substituted or unsubstituted cyclic alkyl, C₁ -C₃₀ substituted or unsubstituted linear alkoxy, C₃ -C₃₀ substituted or unsubstituted branched alkoxy, C₃ -C₃₀ substituted or unsubstituted cyclic alkoxy, C₂ -C₃₀ substituted or unsubstituted linear alkenyl, C₃ -C₃₀ substituted or unsubstituted branched alkenyl, C₃ -C₃₀ substituted or unsubstituted cyclic alkenyl, C₂ -C₃₀ substituted or unsubstituted linear alkynyl, C₃ -C₃₀ substituted or unsubstituted branched alkynyl, C₆ -C₃₀ substituted or unsubstituted alkylenearyl; or R⁴, R⁵, and R⁶ can be taken together to form C₆ -C₃₀ substituted or unsubstituted aryl; and mixtures thereof.

Preferably at least two R¹, R², or R³ units are hydrogen. Preferably when two R⁴, R⁵, and R⁶ units are hydrogen, the remaining unit is C₁ -C₂₀ substituted or unsubstituted linear alkyl, C₃ -C₂₀ substituted or unsubstituted branched alkyl, C₃ -C₂₀ substituted or unsubstituted cyclic alkyl; more preferably methyl. Also preferably R⁴, R⁵, and R⁶ are taken together to form a C₆ -C₃₀ substituted or unsubstituted aryl units, preferably substituted or unsubstituted phenyl and naphthyl.

For the purposes of the present invention the term "substituted" as it applies to linear alkyl, branched alkyl, cyclic alkyl, linear alkenyl, branched alkenyl, cyclic alkenyl, alkynyl, and branched alkynyl units are defined as "carbon chains which comprise substitutents other than branching of the carbon atom chain", for example, other than the branching of alkyl units (e.g. isopropyl, isobutyl). Non-limiting examples of "substituents" include hydroxy, C₁ -C₁₂ alkoxy, preferably methoxy; C₃ -C₁₂ branched alkoxy, preferably isopropoxy; C₃ -C₁₂ cyclic alkoxy; nitrilo; halogen, preferably chloro and bromo, more preferably chloro; nitro; morpholino; cyano; carboxyl, non-limiting examples of which are --CHO; --CO₂ --M⁺, --CO₂ R⁹ ; --CONH₂ ; --CONHR⁹ ; --CONR⁹ ₂ ; wherein R⁹ is C₁ -C₁₂ linear or branched alkyl); --SO₃ ⁻ M⁺ ; --OSO₃ ⁻ M⁺ ; --N(R¹⁰)₂ ; and --N⁺ (R¹⁰)₃ X⁻ wherein each R¹⁰ is independently hydrogen or C₁ -C₄ alkyl; and mixtures thereof; wherein M is hydrogen or a water soluble cation; and X is chlorine, bromine, iodine, or other water soluble anion.

For the purposes of the present invention substituted or unsubstituted alkyleneoxy units are defined as moieties having the formula: ##STR4## wherein R⁷ is hydrogen; R⁸ is hydrogen, methyl, ethyl, and mixtures thereof; the index x is from 1 to about 20.

For the purposes of the present invention substituted or unsubstituted alkyleneoxyalkyl are defined as moieties having the formula: ##STR5## wherein R⁷ is hydrogen, C₁ -C₁₈ alkyl, C₁ -C₄ alkoxy, and mixtures thereof; R⁸ is hydrogen, methyl, ethyl, and mixtures thereof; the index x is from 1 to about 20 and the index y is from 2 to about 30.

For the purposes of the present invention substituted or unsubstituted aryl units are defined as phenyl moieties having the formula: ##STR6## or α and β-naphthyl moieties having the formula: ##STR7## wherein R⁷ and R⁸ can be substituted on either ring, alone or in combination, and R⁷ and R⁸ are each independently hydrogen, hydroxy, C₁ -C₆ alkyl, C₂ -C₆ alkenyl, C₁ -C₄ alkoxy, C₃ -C₆ branched alkoxy, nitrilo, halogen, nitro, morpholino, cyano, carboxyl (--CHO; --CO₂ ⁻ M⁺ ; --CO₂ R⁹ ; --CONH₂ ; --CONHR⁹ ; --CONR⁹ ₂ ; wherein R⁹ is C₁ -C₁₂ linear or branched alkyl), --SO₃ ⁻ M⁺, --OSO₃ ⁻ M⁺, --N(R¹⁰)₂, and --N⁺ (R¹⁰)₃ X⁻ wherein each R¹⁰ is independently hydrogen or C₁ -C₄ alkyl; and mixtures thereof; and mixtures thereof, R⁷ and R⁸ are preferably hydrogen C₁ -C₆ alkyl, --CO₂ ⁻ M⁺, --SO₃ ⁻ M⁺, --OSO₃ ⁻ M⁺, and mixtures thereof, more preferably R⁷ or R⁸ is hydrogen and the other moiety is C₁ -C₆ ; wherein M is hydrogen or a water soluble cation and X is chlorine, bromine, iodine, or other water soluble anion. Examples of other water soluble anions include organic species such as fumarate, tartrate, oxalate and the like, inorganic species include sulfate, hydrogen sulfate, phosphate and the like.

For the purposes of the present invention substituted or unsubstituted alkylenearyl units are defined as moieties having the formula: ##STR8## wherein R⁷ and R⁸ are each independently hydrogen, hydroxy, C₁ -C₄ alkoxy, nitrilo, halogen, nitro, carboxyl (--CHO; --CO₂ ⁻ M⁺ ; --CO₂ R'; --CONH₂ ; --CONHR'; --CONR'₂ ; wherein R' is C₁ -C₁₂ linear or branched alkyl), amino, alkylamino, and mixtures thereof, p is from 1 to about 34; M is hydrogen or a water soluble cation.

For the purposes of the present invention substituted or unsubstituted alkyleneoxyaryl units are defined as moieties having the formula: ##STR9## wherein R⁷ and R⁸ are each independently hydrogen, hydroxy, C₁ -C₄ alkoxy, nitrilo, halogen, nitro, carboxyl (--CHO; --CO₂ ⁻ M⁺ ; --CO₂ R⁹ ; --CONH₂ ; --CONHR⁹ ; --CONR⁹ ₂ ; wherein R⁹ is C₁ -C₁₂ linear or branched alkyl), amino, alkylamino, and mixtures thereof, q is from 1 to about 34; M is hydrogen or a water soluble cation.

Surprisingly, the pro-accords which comprise the fragrance delivery systems of the present invention are capable of releasing at least one fragrance raw material, preferably the pro-accords release two or more fragrance raw materials. For example, the pro-accord 3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-propionate having the formula: ##STR10## releases, depending upon usage conditions, at least two fragrance raw materials inter alia linalool, β-naphthyl methyl ketone, myrcene, α-terpinolene, and Δ-3-carene.

The pro-accords which comprise the fragrance delivery systems of the present invention are capable of releasing their fragrance compounds by more than a single chemical mechanism, a point which is key to the variety of fragrance raw materials which are released from a single pro-accord compound. However, depending upon the desires of the formulator, the pro-accords of the present invention are capable of releasing a different mixture of fragrance raw materials depending upon the releasing milieu. For example, the pro-accord 3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-propionate produces a different accord when undergoing fragrance raw material release in water than when said pro-accord is subjected to the high temperature typical of an automatic clothes dryer. Typically the pro-accords of the present invention release a mixture of alcohols, esters, ketones, hydrocarbyl materials, especially terpenes, having aesthetically pleasing qualities, and mixtures thereof. For the purposes of the present invention the term "hydrocarbyl material" is defined as a compound which essentially comprises only carbon and hydrogen inter alia alkanes, alkenes, and alkynes whether linear, cyclic, branched, or combinations thereof". An example, of a hydrocarbyl material which is capable of being released by a pro-accord of the present invention is α-pinene. For the purposes of the present invention the term "terpene" is used to designate hydrocarbons inter alia myrcene, limonene, and α-terpinene. However, those skilled in the art of perfumes as well as organic chemistry recognize that geraniol and nerol which are listed under "fragrance raw material alcohols" herein above are also terpenes. Throughout the present specification the term "terpene" is used interchangably with "hydrocarbyl" and is used broadly, when it refers to all alcohols, ketones, alkenes, etc. that are generally regarded as terpenes, and narrowly when refering primarily to alkanes, alkenes, etc. having typically 10 or 15 carbon atoms.

Examples of alcohols releasable by the pro-accords are described herein above and are typically the fragrance raw material alcohols which are used to form the parent compounds. However, during the process of fragrance raw material release, these fragrance raw material alcohols are capable of undergoing further modification, including isomerization and/or rearrangement. Therefore, in addition to the original alcohol used to form the parent pro-accord ester, additional alcohols may be formed by transformations which occur during the release process. Depending upon the choices the formulator makes when designing the pro-accord molecules in formulating a fragrance delivery system according to the present invention, these transformations can take place to a greater or lesser degree.

Non-limiting examples of terpenes releasable by the pro-accords of the present invention include myrcene, ocimene, β-farnesene, cis-achillene, trans-achillene, carvomenthene, limonene, α-terpinene, γ-terpinene, terpinolene, αphellandrene, β-phellandrene, 2-carene, 3-carene, α-pinene, β-pinene, camphene, (-)-(2S,4R)-2-(2-methyl-1-propenyl)-4-methyltetrahydropyran (cis rose oxide), (-)-(2S,4S)-2-(2-methyl-1-propenyl)-4-methyltetrahydropyran (trans rose oxide), 2-methyl-2-vinyl-5-(a-hydroxyisopropyl)tetrahydrofuran (linalool oxide), and mixtures thereof.

Non-limiting examples of preferred β-ketoester pro-fragrances include 3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-propionate, [linalyl (2-naphthoyl)-acetate], having the formula: ##STR11## 3,7-dimethyl-1,6-octadien-3-yl 3-(α-naphthyl)-3-oxo-propionate, [linalyl (1-naphthoyl)acetate], having the formula: ##STR12## 2,6-dimethyl-7-octen-2-yl 3-(4-methoxyphenyl)-3-oxo-propionate, [3-(4-methoxyphenyl)-3-oxo-propionic acid dihydromyrcenyl ester], having the formula: ##STR13## 2,6-dimethyl-7-octen-2-yl 3-(4-nitrophenyl)-3-oxo-propionate, [3-(4-nitrophenyl)-3-oxo-propionic acid dihydromyrcenyl ester], having the formula: ##STR14## 2,6-dimethyl-7-octen-2-yl 3-(β-naphthyl)-3-oxo-propionate, [dihydromyrcenyl (2-naphthoyl)acetate], having the formula: ##STR15## 3,7-dimethyl-1,6-octadien-3-yl 3-(4-methoxyphenyl)-3-oxo-propionate, [3-(4-methoxyphenyl)-3-oxo-propionic acid linalyl ester], having the formula: ##STR16## (α,α-4-trimethyl-3-cyclohexenyl)methyl 3-(β-naphthyl)-3-oxo-propionate, [α-terpinyl (2-naphthoyl)acetate], having the formula: ##STR17## 9-decen-1-yl 3-(β-naphthyl)-3-oxo-propionate, [9-decen-1-yl (2-naphthoyl)acetate], known alternatively as, roslava 2'-acetonaphthone, having the formula: ##STR18## 3,7-dimethyl-1,6-octadien-3-yl 3-(nonanyl)-3-oxo-propionate, [linalyl (nonanoyl)acetate], known alternatively as, octyl [(linalyl) α-acetyl] ketone, having the formula: ##STR19##

Further examples of preferred β-ketoester pro-fragrances include 3,7-dimethyl-1,6-octadien-3-yl 3-oxo-butyrate, 2,6-dimethyl-7-octen-2-yl 3-oxo-butyrate, 6-heptyl-5-hepten-2-yl 3-oxo-butyrate, 1-(prop-2-enyl)cyclopentanyl 3-oxo-butyrate, (α,α-4-trimethyl-3-cyclohexenyl)methyl 3-oxo-butyrate, cis-3-hexenyl 3-oxo-butyrate, and mixtures thereof.

The β-keto-esters of the present invention are exemplified by, but limited to, the following synthetic scheme: ##STR20##

The compositions of the present invention also include β-keto-esters formed from derivatives of blends of 2 or more parent alcohols. In such a case, a distribution of varying R¹ groups attached to the same R moiety can be obtained in a "one-pot" synthesis. This blend can generate a fragrance "accord" in an economical, consistent and straightforward manner.

B. Fabric Softening Compound

Compositions of the present invention contain from about 10% to about 99.99%, preferably from about 15% to about 90%, more preferably from about 30% to about 85%, and even more preferably from about 30% to about 55%, of fabric softening compound, preferably ester quaternary ammonium compound (EQA).

Preferably, the EQA of the present invention is selected from Formulas I, II, III, IV, and mixtures thereof.

Formula I comprises:

    (R.sup.1).sub.4-p --N.sup.+ --((CH.sub.2).sub.v --Y--R.sup.2).sub.p X.sup.-

wherein

each Y=--O--(O)C--, or --C(O)--O--;

p=1 to 3;

each v=is an integer from 1 to 4, and mixtures thereof;

each R¹ substituent is a short chain C₁ -C₆, preferably C₁ -C₃, alkyl group, e.g., methyl (most preferred), ethyl, propyl, and the like, benzyl and mixtures thereof;

each R² is a long chain, saturated and/or unsaturated (IV of from about 3 to about 60), C₈ -C₃₀ hydrocarbyl, or substituted hydrocarbyl substituent and mixtures thereof; and the counterion, X⁻, can be any softener-compatible anion, for example, methylsulfate, ethylsulfate, chloride, bromide, formate, sulfate, lactate, nitrate, benzoate, and the like, preferably methylsulfate.

It will be understood that substituents R¹ and R² of Formula I can optionally be substituted with various groups such as alkoxyl or hydroxyl groups. The preferred compounds can be considered to be diester (DEQA) variations of ditallow dimethyl ammonium methyl sulfate (DTDMAMS), which is a widely used fabric softener. At least 80% of the DEQA is in the diester form, and from 0% to about 20%, preferably less than about 10%, more preferably less than about 5%, can be EQA monoester (e.g., only one --Y--R² group).

As used herein, when the diester is specified, it will include the monoester that is normally present. For the optimal antistatic benefit the percentage of monoester should be as low as possible, preferably less than about 2.5%. The level of monoester present can be controlled in the manufacturing of the EQA.

EQA compounds prepared with fully saturated acyl groups are rapidly biodegradable and excellent softeners. However, it has now been discovered that compounds prepared with at least partially unsaturated acyl groups have advantages (i.e., antistatic benefits) and are highly acceptable for consumer products when certain conditions are met.

Variables that must be adjusted to obtain the benefits of using unsaturated acyl groups include the Iodine Value of the fatty acids, the odor of fatty acid starting material, and/or the EQA. Any reference to Iodine Value values hereinafter refers to Iodine Value of fatty acyl groups and not to the resulting EQA compound.

Antistatic effects are especially important where the fabrics are dried in a tumble dryer, and/or where synthetic materials which generate static are used. As the Iodine Value is raised, there is a potential for odor problems.

Some highly desirable, readily available sources of fatty acids such as tallow, possess odors that remain with the compound EQA despite the chemical and mechanical processing steps which convert the raw tallow to finished EQA. Such sources must be deodorized, e.g., by absorption, distillation (including stripping such as steam stripping), etc., as is well known in the art. In addition, care must be taken to minimize contact of the resulting fatty acyl groups to oxygen and/or bacteria by adding antioxidants, antibacterial agents, etc. The additional expense and effort associated with the unsaturated fatty acyl groups is justified by the superior performance which has not been recognized.

Generally, hydrogenation of fatty acids to reduce polyunsaturation and to lower Iodine Value to insure good color and odor stability leads to a high degree of trans configuration in the molecule. Therefore, diester compounds derived from fatty acyl groups having low Iodine Value values can be made by mixing fully hydrogenated fatty acid with touch hydrogenated fatty acid at a ratio which provides an Iodine Value of from about 3 to about 60. The polyunsaturation content of the touch hardened fatty acid should be less than about 5%, preferably less than about 1%. During touch hardening the cis/trans isomer weight ratios are controlled by methods known in the art such as by optimal mixing, using specific catalysts, providing high H₂ availability, etc.

It has been found that a solvent may be used to facilitate processing of the Formula I EQA and/or of the fabric softening composition containing the Formula I EQA. Possible solvents include C₁ -C₃₀ alcohols, with secondary and tertiary alcohols preferred, e.g., isopropanol, and C₈ -C₃₀ fatty acids.

It has also been found that for good chemical stability of the diester quaternary compound in molten storage, water levels in the raw material must be minimized to preferably less than about 1% and more preferably less than about 0.5%. Storage temperatures should be kept as low as possible and still maintain a fluid material, ideally in the range of from about 45° C. to about 70° C. The optimum storage temperature for stability and fluidity depends on the specific Iodine Value of the fatty acid used to make the diester quaternary and the level/type of solvent selected. Also, exposure to oxygen should be minimized to keep the unsaturated groups from oxidizing. It can therefore be important to store the material under a reduced oxygen atmosphere such as a nitrogen blanket. It is important to provide good molten storage stability to provide a commercially feasible raw material that will not degrade noticeably in the normal transportation/storage/handling of the material in manufacturing operations.

The following are non-limiting examples of EQA Formula I (wherein all long-chain alkyl substituents are straight-chain):

Saturated ##STR21## where --C(O)R² is derived from saturated tallow.

Unsaturated ##STR22## where --C(O)R² is derived from partially hydrogenated tallow or modified tallow having the characteristics set forth herein.

In addition to Formula I compounds, the compositions and articles of the present invention comprise EQA compounds of Formula II: ##STR23## wherein, for any molecule: each Q is ##STR24## each R¹ is C₁ -C₄ alkyl or hydroxy alkyl; R² and v are defined hereinbefore for Formula I; and

wherein preferably R¹ is a methyl group, v is 1, Q is ##STR25## each R² is C₁₄ -C₁₈, and X⁻ is methyl sulfate.

The straight or branched alkyl or alkenyl chains, R², have from about 8 to about 30 carbon atoms, preferably from about 14 to about 18 carbon atoms, more preferably straight chains having from about 14 to about 18 carbon atoms.

Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl materials.

A specific example of a biodegradable Formula II EQA compound suitable for use in the fabric softening compositions herein is: 1,2-bis(tallowyl oxy)-3-trimethyl ammoniopropane methylsulfate (DTTMAPMS).

Other examples of suitable Formula II EQA compounds of this invention are obtained by, e.g., replacing "tallowyl" in the above compounds with, for example, cocoyl, lauryl, oleyl, stearyl, palmityl, or the like;

replacing "methyl" in the above compounds with ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, or the hydroxy substituted analogs of these radicals;

replacing "methylsulfate" in the above compounds with chloride, ethylsulfate, bromide, formate, sulfate, lactate, nitrate, and the like, but methylsulfate is preferred.

In addition to Formula I and Formula II compounds, the compositions and articles of the present invention comprise EQA compounds of Formula III: ##STR26## wherein R⁴ =a short chain C₁ -C₄ alcohol;

p is 2;

R¹, R², v, Y, and X⁻ are as previously defined for Formula I.

A specific example of a biodegradable Formula III compound suitable for use in the fabric softening compositions herein is N-methyl-N,N-di-(2-(C₁₄ -C₁₈ -acyloxy) ethyl), N-2-hydroxyethyl ammonium methylsulfate. A preferred compound is N-methyl, N,N-di-(2-oleyloxyethyl) N-2-hydroxyethyl ammonium methylsulfate.

Compositions of the present invention may also comprise Formula IV compounds:

    (R.sup.1).sub.4-p --N.sup.+ --((CH.sub.2).sub.v --Y"--R.sup.2).sub.p X.sup.-

R¹, R², p, v, and X are previously defined in Formula I; and ##STR27## wherein at least one Y" group is ##STR28## An example of this compound is methyl bis (oleyl amidoethyl) 2-hydroxyethyl ammonium methyl sulfate.

Preferably, Component (A) of the present invention is a biodegradable quaternary ammonium compound.

The compounds herein can be prepared by standard esterification and quaternization reactions, using readily available starting materials. General methods for preparation are disclosed in U.S. Pat. No. 4,137,180, incorporated herein by reference.

C. Optional Ingredients

Well known optional components included in fabric conditioning compositions are narrated in U.S. Pat. No. 4,103,047, Zaki et al., issued Jul. 25, 1978, for "Fabric Treatment Compositions," incorporated herein by reference.

(1) Co-Softener

Fabric softening compositions employed herein contain as an optional component, at a level of from about 0% to about 95%, preferably from about 20% to about 75%, more preferably from about 20% to about 60%, a carboxylic acid salt of a tertiary amine and/or ester amine which has the formula: ##STR29## wherein R⁵ is a long chain aliphatic group containing from about 8 to about 30 carbon atoms; R⁶ and R⁴ are the same or different from each other and are selected from the group consisting of aliphatic groups containing containing from about 1 to about 30 carbon atoms, hydroxyalkyl groups of the Formula R⁸ OH wherein R⁸ is an alkylene group of from about 2 to about 30 carbon atoms, and alkyl ether groups of the formula R⁹ O(C_(n) H_(2n) O)_(m) wherein R⁹ is alkyl and alkenyl of from about 1 to about 30 carbon atoms and hydrogen, n is 2 or 3, and m is from about 1 to about 30; wherein R⁴, R⁵, R⁶, R⁸, and R⁹ chains can be ester interrupted groups; and wherein R⁷ is selected from the group consisting of unsubstituted alkyl, alkenyl, aryl, alkaryl and aralkyl of about 8 to about 30 carbon atoms, and substituted alkyl, alkenyl, aryl, alkaryl, and aralkyl of from about 1 to about 30 carbon atoms wherein the substituents are selected from the group consisting of halogen, carboxyl, and hydroxyl, said composition having a thermal softening point of from about 35° C. to about 100° C.

This essential component provides the following benefits: superior odor, and/or improved fabric softening performance, compared to similar articles which utilize primary amine or ammonium compounds as the sole fabric conditioning agent. Either R⁴, R⁵, R⁶, R⁷, R⁸, and/or R⁹ chains can contain unsaturation.

Additionally, tertiary amine salts of carboxylic acids have superior chemical stability, compared to primary and secondary amine carboxylate salts. For example, primary and secondary amine carboxylates tend to form amides when heated, e.g., during processing or use in the dryer. Also, they absorb carbon dioxide, thereby forming high melting carbamates which build up as an undesirable residue on treated fabrics.

Preferably, R⁵ is an aliphatic chain containing from about 12 to about 30 carbon atoms, R⁶ is an aliphatic chain of from about 1 to about 30 carbon atoms, and R⁴ is an aliphatic chain of from about 1 to about 30 carbon atoms. Particularly preferred tertiary amines for static control performance are those containing unsaturation; e.g., oleyldimethylamine and/or soft tallowdimethylamine.

Examples of preferred tertiary amines as starting material for the reaction between the amine and carboxylic acid to form the tertiary amine salts are: lauryldimethylamine, myristyldimethylamine, stearyldimethylamine, tallowdimethylamine, coconutdimethylamine, dilaurylmethylamine, distearylmethylamine, ditallowmethylamine, oleyldimethylamine, dioleylmethylamine, lauryldi(3-hydroxypropyl)amine, stearyldi(2-hydroxyethyl)amine, trilaurylamine, laurylethylmethylamine, and ##STR30## Preferred fatty acids are those wherein R⁷ is a long chain, unsubstituted alkyl or alkenyl group of from about 8 to about 30 carbon atoms, more preferably from about 11 to about 17 carbon atoms.

Examples of specific carboxylic acids as a starting material are: formic acid, acetic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, oxalic acid, adipic acid, 12-hydroxy stearic acid, benzoic acid, 4-hydroxy benzoic acid, 3-chloro benzoic acid, 4-nitro benzoic acid, 4-ethyl benzoic acid, 4-(2-chloroethyl)benzoic acid, phenylacetic acid, (4-chlorophenyl)acetic acid, (4-hydroxyphenyl)acetic acid, and phthalic acid.

Preferred carboxylic acids are stearic, oleic, lauric, myristic, palmitic, and mixtures thereof.

The amine salt can be formed by a simple addition reaction, well known in the art, disclosed in U.S. Pat. No. 4,237,155, Kardouche, issued Dec. 2, 1980, which is incorporated herein by reference. Excessive levels of free amines may result in odor problems, and generally free amines provide poorer softening performance than the amine salts.

Preferred amine salts for use herein are those wherein the amine moiety is a C₈ -C₃₀ alkyl or alkenyl dimethyl amine or a di-C₈ -C₃₀ alkyl or alkenyl methyl amine, and the acid moiety is a C₈ -C₃₀ alkyl or alkenyl monocarboxylic acid. The amine and the acid, respectively, used to form the amine salt will often be of mixed chain lengths rather than single chain lengths, since these materials are normally derived from natural fats and oils, or synthetic processed which produce a mixture of chain lengths. Also, it is often desirable to utilize mixtures of different chain lengths in order to modify the physical or performance characteristics of the softening composition.

Specific preferred amine salts for use in the present invention are oleyldimethylamine stearate, stearyldimethylamine stearate, stearyldimethylamine myristate, stearyldimethylamine oleate, stearyldimethylamine palmitate, distearylmethylamine palmitate, distearylmethylamine laurate, and mixtures thereof. A particularly preferred mixture is oleyldimethylamine stearate and distearylmethylamine myristate, in a ratio of 1:10 to 10:1, preferably about 1:1.

(2) Optional Nonionic Softener

An optional softening agent of the present invention is a nonionic fabric softener material. Typically, such nonionic fabric softener materials have an HLB of from about 2 to about 9, more typically from about 3 to about 7. In general, the materials selected should be relatively crystalline, higher melting, (e.g., >25° C.).

The level of optional nonionic softener in the solid composition is typically from about 10% to about 50%, preferably from about 15% to about 40%.

Preferred nonionic softeners are fatty acid partial esters of polyhydric alcohols, or anhydrides thereof, wherein the alcohol, or anhydride, contains from about 2 to about 18, preferably from about 2 to about 8, carbon atoms, and each fatty acid moiety contains from about 8 to about 30, preferably from about 12 to about 20, carbon atoms. Typically, such softeners contain from about one to about 3, preferably about 2 fatty acid groups per molecule.

The polyhydric alcohol portion of the ester can be ethylene glycol, glycerol, poly (e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.

The fatty acid portion of the ester is normally derived from fatty acids having from about 8 to about 30, preferably from about 12 to about 22, carbon atoms. Typical examples of said fatty acids being lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid.

Highly preferred optionally nonionic softening agents for use in the present invention are C₁₀ -C₂₆ acyl sorbitan esters and polyglycerol monostearate. Sorbitan esters are esterified dehydration products of sorbitol. The preferred sorbitan ester comprises a member selected from the group consisting of C₁₀ -C₂₆ acyl sorbitan monoesters and C₁₀ -C₂₆ acyl sorbitan diesters and ethoxylates of said esters wherein one or more of the unesterified hydroxyl groups in said esters contain from 1 to about 6 oxyethylene units, and mixtures thereof. For the purpose of the present invention, sorbitan esters containing unsaturation (e.g., sorbitan monooleate) can be utilized.

Sorbitol, which is typically prepared by the catalytic hydrogenation of glucose, can be dehydrated in well known fashion to form mixtures of 1,4- and 1,5-sorbitol anhydrides and small amounts of isosorbides. (See U.S. Pat. No. 2,322,821, Brown, issued Jun. 29, 1943, incorporated herein by reference.)

The foregoing types of complex mixtures of anhydrides of sorbitol are collectively referred to herein as "sorbitan." It will be recognize that this "sorbitan" mixture will also contain some free, uncyclized sorbitol.

The preferred sorbitan softening agents of the type employed herein can be prepared by esterifying the "sorbitan" mixture with a fatty acyl group in standard fashion, e.g., by reaction with a fatty acid halide, fatty acid ester, and/or fatty acid. The esterification reaction can occur at any of the available hydroxyl groups, and various mono-, di-, etc., esters can be prepared. In fact, mixtures of mono-, di-, tri-, etc., esters almost always result from such reactions, and the stoichiometric ratios of the reactants can be simply adjusted to favor the desired reaction product.

For commercial production of the sorbitan ester materials, etherification and esterification are generally accomplished in the same processing step by reacting sorbitol directly with fatty acids. Such a method of sorbitan ester preparation is described more fully in MacDonald; "Emulsifiers:" Processing and Quality Control:, Journal of the American Oil Chemists' Society, Vol. 45, October 1968.

Details, including formula, of the preferred sorbitan esters can be found in U.S. Pat. No. 4,128,484, incorporated hereinbefore by reference.

Certain derivatives of the preferred sorbitan esters herein, especially the "lower" ethoxylates thereof (i.e., mono- , di-, and tri-esters wherein one or more of the unesterified --OH groups contain one to about twenty oxyethylene moieties (Tweens®) are also useful in the composition of the present invention. Therefore, for purposes of the present invention, the term "sorbitan ester" includes such derivatives.

For the purposes of the present invention, it is preferred that a significant amount of di- and tri- sorbitan esters are present in the ester mixture. Ester mixtures having from 20-50% mono-ester, 25-50% di-ester and 10-35% of tri- and tetra-esters are preferred.

The material which is sold commercially as sorbitan mono-ester (e.g., monostearate) does in fact contain significant amounts of di- and tri-esters and a typical analysis of sorbitan monostearate indicates that it comprises about 27% mono-, 32% di- and 30% tri- and tetra-esters. Commercial sorbitan monostearate therefore is a preferred material. Mixtures of sorbitan stearate and sorbitan palmitate having stearate/palmitate weight ratios varying between 10:1 and 1:10, and 1,5-sorbitan esters are useful. Both the 1,4- and 1,5- sorbitan esters are useful herein.

Other useful alkyl sorbitan esters for use in the softening compositions herein include sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan monooleate, sorbitan dilaurate, soritan dimyristate, sorbitan dipalmitate, sorbitan disterate, sorbitan dibehenate, sorbitan dioleate, and mixtures thereof, and mixed tallowalkyl sorbitan mono- and di-esters. Such mixtures are readily prepared by reacting the foregoing hydroxy-substituted sorbitans, particularly the 1,4- and 1,5-sorbitans, with the corresponding acid, ester, or acid chloride in a simple esterification reaction. It is to be recognized, of course, that commercial materials prepared in this manner will comprise mixtures usually containing minor proportions of uncyclized sorbitol, fatty acids, polymers, isosorbide structures, and the like. In the present invention, it is preferred that such impurities are present at as low a level as possible.

The preferred sorbitan esters employed herein can contain up to about 15% by weight of esters of the C₂₀ -C₂₆, and higher, fatty acids, as well as minor amounts of C₈, and lower, fatty esters.

Glycerol and polyglycerol esters, especially glycerol, diglycerol, triglycerol, and polyglycerol mono- and/or di- esters, preferably mono- , are also preferred herein (e.g., polyglycerol monostearate with a trade name of Radiasurf 7248). Glycerol esters can be prepared from naturally occurring triglycerides by normal extraction, purification and/or intersterification processes or by esterification processes of the type set forth hereinbefore for sorbitan esters. Partial esters of glycerin can also be ethoxylated to form usable derivatives that are included within the term "glycerol esters."

Useful glycerol and polyglcyerol esters include mono-esters with stearic, oleic, palmitic, lauric, isostearic, myristic, and/or behenic acids and the diesters of stearic, oleic, palmitic, lauric, isostearic, behenic, and/or myristic acids. It is understood that the typical mono-ester contains some di- and tri-ester, etc.

The "glcyerol esters" also include the polyglycerol, e.g., diglycerol through octaglycerol esters. The polyglycerol polyols are formed by condensing glycerin or epichlorohydrin together to link the glycerol moieties via ether linkages. The mono- and/or diesters of the polyglycerol polyols are preferred, the fatty acyl groups typically being those described hereinbefore for the sorbitan and glycerol esters.

(3) Optional Soil Release Agent

Optionally, the compositions herein contain from 0% to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.1% to about 2%, of a soil release agent. Preferably, such a soil release agent is a polymer. Polymeric soil release agents useful in the present invention include copolymeric blocks of terephthalate and polyethylene oxide or polypropylene oxide, and the like. U.S. Pat. No. 4,956,447, Gosselink/Hardy/Trinh, issued Sep. 11, 1990, discloses specific preferred soil release agents comprising cationic functionalities, said patent being incorporated herein by reference.

A preferred soil release agent is a copolymer having blocks of terephthalate and polyehtylene oxide. More specifically, these polymers are comprised of repeating units of ethylene and/or propylene terephthalate and polyethylene oxide terephthalate at a molar ratio of ethylene terephthalate units to polyethylene oxide terephthalate units of from about 25:75 to about 35:65; said polyehtylene oxide terephthalate containing polyethylene oxide blocks having molecular weights of from about 300 to about 2000. The molecular weight of this polymeric soil release agents is in the range of from about 5,000 to about 55,000.

U.S. Pat. No. 4,976,879, Maldonado/Trinh/Gosselink, issued Dec. 11, 1990, discloses specific preferred soil release agents which can also provide improved antistat benefit, said patent being incorporated herein by reference.

Another preferred polymeric soil release agent is a crystallizable polyester with repeat units of ethylene terephthalate units containing from about 10% to about 15% by weight of ethylene terephthalate units together with from about 10% to about 50% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight of from about 300 to about 6,000, and the molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the crystallizable polymeric compound is between 2:1 and 6:1. Examples of this polymer include the commercially available materials Zelcon® 4780 (from DuPont) and Milease® T (from ICI).

A more complete disclosure of these highly preferred soil release agents is contained in European Pat. Application 185,427, Gosselink, published Jun. 25, 1986, incorporated herein by reference.

(4) Optional Cyclodextrin/Perfume Complexes and Free Perfume

The products herein can also contain from about 0% to about 60%, preferably from about 0.5% to about 60%, more preferably from about 1% to about 50%, cyclodextrin/perfume inclusion complexes and/or free perfume, as disclosed in U.S. Pat. Nos. 5,139,687, Borcher et al., issued Aug. 18, 1992; and 5,234,610, Gardlik et al., to issue Aug. 10, 1993, which are incorporated herein by reference. Perfumes are highly desirable, can usually benefit from protection, can be complexed with cyclodextrin. Fabric softening products typically contain perfume to provide an olfactory aesthetic benefit and/or to serve as a signal that the product is effective.

The optional perfume ingredients and compositions of this invention are the conventional ones known in the art. Selection of any perfume component, or amount of perfume, is based solely on aesthetic considerations. Suitable perfume compounds and compositions can be found in the art including U.S. Pat. Nos.: 4,145,184, Brain and Cummins, issued Mar. 20, 1979; 4,209,417, Whyte issued Jun. 24, 1980; 4,515,705, Moeddel, issued May 7, 1985; and 4,152,272, Young, issued May 1, 1979, all of said patents being incorporated herein by reference. Many of the art recognized perfume compositions are relatively substantive to maximize their odor effect on substrates. However, it is a special advantage of perfume delivery via the perfume/cyclodextrin complexes that nonsubstantive perfumes are also effective.

If a product contains both free and complexed perfume, the escaped perfume from the complex contributes to the overall perfume odor intensity, giving rise to a longer lasting perfume odor impression.

As disclosed in U.S. Pat. No. 5,234,610, Gardlik/Trinh/Banks/Benvegnu, issued Aug. 3, 1993, said patent being incorporated herein by reference, by adjusting the levels of free perfume and perfume/CD complex it is possible to provide a wide range of unique perfume profiles in terms of timing (release) and/or perfume identity (character). Solid, dryer-activated fabric conditioning compositions are a uniquely desirable way to apply the cyclodextrins, since they are applied at the very end of a fabric treatment regimen when the fabric is clean and when there are almost no additional treatments that can remove the cyclodextrin.

(5) Stabilizers

Stabilizers can be present in the compositions of the present invention. The term "stabilizer, " as used herein, includes antioxidants and reductive agents. These agents are present at a level of from 0% to about 2%, preferably from about 0.01% to about 0.2%, more preferably from about 0.05% to about 0.1% for antioxidants and more preferably from about 0.01% to about 0.2% for reductive agents. These assure good odor stability under long term storage conditions for the compositions. Use of antioxidants and reductive agent stabilizers is especially critical for unscented or low scent products (no or low perfume).

Examples of antioxidants that can be added to the compositions of this invention include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate, available from Eastman Chemical Products, Inc., under the trade names Tenox® PG and Tenox S-1; a mixture of BHT, BHA, propyl gallate, and citric acid available from Eastman Chemicals Products, Inc., under the trade name Tenox-6; butylated hydroxytoluene, available from UOP Process Division under the trade name Sustane® BHT; tertiary butylhydroquinone, Eastman Chemical Products, Inc., as Tenox TBHQ; natural tocopherols, Eastman Chemical Products, Inc., as Tenox GT-1/GT-2; and butylated hydroxyanisole, Eastman Chemical Products, Inc., as BHA.

Examples of reductive agents include sodium borohydride, hypophosphorous acid, and mixtures thereof.

(6) Other Optional Ingredients

The present invention can include other optional components (minor components) conventionally used in textile treatment compositions, for example, colorants, preservatives, optical brighteners, opacifiers, stabilizers such as guar gum and polyethylene glycol, anti-shrinkage agents, anti-wrinkle agents, fabric crisping agents, spotting agents, germicides, fungicides, anti-corrosion agents, antifoam agents, and the like.

D. Substrate Articles

In preferred embodiments, the present invention compasses articles of manufacture. Representative articles are those that are adapted to soften fabrics in an automatic laundry dryer, of the types disclosed in U.S. Pat. Nos: 3,989,,631 Marsan, issued Nov. 2, 1976; 4,055,248, Marsan, issued Oct. 25, 1977; 4,073,996, Bedenk et al., issued Feb. 14, 1978; 4,022,938, Zaki et al., issued May 10, 1977, 4,764,289, Trinh, issued Aug. 16, 1988; 4,808,086, Evans, et al., issued Feb. 28, 1989; 4,103,047, Zaki et al., issued Jul. 25, 1978; 3,736,668, Dillarstone, issued Jun. 5, 1973; 3,701,202, Compa et al., issued Oct. 31, 1972; 3,634,947, Furgal, issued Jan. 18, 1972; 3,633,538, Hoeflin, issued Jan. 11, 1972; and 3,435,537, Rumsey, issued Apr. 1, 1969; and 4,000,340, Murphy et al., issued Dec. 28, 1976, all of said patents being incorporated herein by reference.

In a preferred substrate article embodiment, the fabric treatment compositions are provided as an article of manufacture in combination with a dispensing means such as a flexible substrate which effectively releases the composition in an automatic laundry (clothes) dryer. Such dispensing means can be designed for single usage or for multiple uses. The dispensing means can also be a "carrier material" that releases the fabric softener composition and then is dispersed and/or exhausted from the dryer.

The dispensing means will normally carry an effective amount of fabric treatment composition. Such effective amount typically provides sufficient fabric conditioning/antistatic agent and/or anionic polymeric soil release agent for at least one treatment of a minimum load in an automatic laundry dryer. Amounts of fabric treatment composition for multiple uses, e.g., up to about 30, can be used. Typical amounts for a single article can vary from about 0.25 g to about 100 g, preferably from about 0.5 g to about 20 g, most preferably from about 1 g to about 10 g.

Highly preferred paper, woven or nonwoven "absorbent" substrates useful herein are fully disclosed in U.S. Pat. No. 3,686,025, Morton, issued Aug. 22, 1972, incorporated herein by reference. It is known that most substances are able to absorb a liquid substance to some degree; however, the term "absorbent" as used herein, is intended to mean a substance with an absorbent capacity (i.e., a parameter representing a substrate's ability to take up and retain a liquid) from 4 to 12, preferably 5 to 7, times its weight of water.

Another article comprises a sponge material releasably enclosing enough fabric treatment composition to effectively impart fabric soil release, antistatic effect and/or softness benefits during several cycles of clothes. This multi-use article can be made by filling a hollow sponge with about 20 grams of the fabric treatment composition.

E. Usage

The substrate embodiment of this invention can be used for imparting the above-described fabric treatment composition to fabric to provide softening and/or antistatic effects to fabric in an automatic laundry dryer. Generally, the method of using the composition of the present invention comprises: commingling pieces of damp fabric by tumbling said fabric under heat in an automatic clothes dryer with an effective amount of the fabric treatment composition. At least the continuous phase of said composition has a melting point greater than about 35° C. and the composition is flowable at dryer operating temperature. This composition comprises from about 10% to about 99.99%, preferably from about 15% to about 90%, of the quaternary ammonium agent selected from the above-defined cationic fabric softeners and mixtures thereof, from about 0% to about 95%, preferably from about 20% to about 75%, more preferably from about 20% to about 60% of the above-defined co-softener.

The present invention relates to improved solid dryer-activated fabric softener compositions which are either (A) incorporated into articles of manufacture in which the compositions are, e.g., on a substrate, or are (B) in the form of particles (including, where appropriate, agglomerates, pellets, and tablets of said particles). Such compositions contain from about 30% to about 95% of normally solid, dryer-softenable material, typically fabric softening agent, containing an effective amount of unsaturation.

In the specification and examples herein, all percentages, ratios and parts are by weight unless otherwise specified and all numerical limits are normal approximations.

The following examples illustrate the esters and compositions of this invention, but are not intended to be limiting thereof.

EXAMPLES OF β-KETO ESTER PERFUME DERIVATIVES Example 1

(±)-Linalyl (2-naphthoyl)acetate

Lithium diisopropylamide in the amount of 101.0 mL (2.0 M, 0.202 mol) is placed into a 500 mL three-necked round-bottomed flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. The flask is placed in a dry ice-acetone bath. Linalyl acetate in the amount of 18.66 g (0.095 mol) is dissolved in THF (5 mL) and the resulting solution added to the flask over 45 min. Once addition is complete, the mixture is stirred for an additional 15 min before being treated with a solution of 2-naphthoyl chloride in the amount of 17.43 g (0.090 mol) dissolved in THF (25 mL) over 30 min. The mixture is warmed to -20° C. and stirred at that temperature for 18 h. After warming to 0° C., the mixture is quenched with 20% HCl (53 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCO₃ solution (2×100 mL), water (2×150 mL) and brine (150 mL), dried over MgSO₄ and filtered. The solvent is removed by rotary evaporation to give an orange/red oil. The oil is purified by column chromatography (elution with 5% ethyl acetate dissolved in petroleum ether) to give an oil. Purity of the product is determined by thin layer chromatography and GC analysis and the structure confirmed by mass spectrometry, ¹ and ¹³ C NMR.

Example 2

Dihyromyrencyl (ρ-anisoyl)acetate N-Isopropylcyclohexylamine in the amount of 25.00 g (0.177 mol) and THF in the amount of 200 mL is placed into a 1000 mL three-necked round-bottomed flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. The flask is placed in a ice-methanol bath cooled to -5° C. and its contents treated with n-butyllithium in the amount of 70.8 mL (2.50 M, 0.177 mol). The mixture is stirred for 20 min and then cooled to -78° C. Dihydromyrcencyl acetate in the amount of 17.55 g (0.089 mol) is dissolved in THF (10 mL) and the resulting solution added to the flask over 45 min. Once addition is complete, the mixture is stirred for an additional 15 min before being treated with a solution of p-anisoyl chloride in the amount of 15.10 g (0.090 mol) dissolved in THF (25 ml) over 30 min and then stirred for 1 h. The mixture is warmed to 0° C. and then treated with 90 mL of 20% HCl an hour later. The mixture is poured into a separatory funnel containing ether (100 ml) and water (200 ml). The aqueous layer is extracted with ether (100 ml). The combined organic layers are washed with saturated NaHCO₃ solution (2×100 ml), water (2×100 ml) and brine (100 ml), dried over MgSO₄ and filtered. The solvent is removed by rotary evaporation to give an orange/red oil. The oil is purified by column chromatography (elution with 5% ethyl acetate dissolved in petroleum ether) to give an oil. Purity of the product is determined by thin layer chromatography and the structure confirmed by ¹ H and ¹³ C NMR.

Example 3

Dihydromyrcenyl (4-nitrobenzoyl)acetate

Lithium diisopropylamide in the amount of 121.0 mL (2.0 M, 0.243 mol) is placed into a 500 mL three-necked round-bottomed flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. The flask is placed in a dry ice-acetone bath. Dihydromyrcenyl acetate in the amount of 22.66 g (0.114 mol) is dissolved in THF (5 mL) and the resulting solution added to the flask over 45 min. Once addition is complete, the mixture is stirred for an additional 15 min before being treated with a solution of 4-nitrobenzoyl chloride in the amount of 20.00 g (0.108 mol) dissolved in THF (25 mL) over 30 min. The mixture is warmed to -20° C. and stirred at that temperature (25 mL) over 30 min. The mixture is warmed to -20° C. and stirred at that temperature for 18 h. After warming to 0° C., the mixture is quenched with 20% HCl (70 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCO₃ solution (2×100 mL), water (2×150 mL) and brine (150 mL), dried over MgSO₄ and filtered. The solvent is removed by rotary evaporation to give an orange/red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate dissolved in petroleum ether) to give a near colorless oil. Purity of the product is determined by thin layer chromatography and the structure confirmed by ¹ H and ¹³ C NMR.

Example 4

Dihydromyrcenyl (2-naphthoyl)acetate

Lithium diisopropylamide in the amount of 100.0 mL (2.0 M, 0.201 mol) is placed into a 500 mL three-necked round-bottomed flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. The flask is cooled to -78° C. Dihydromyrcenyl acetate in the amount of 18.75 g (0.095 mol) is dissolved in THF (5 mL) and the resulting solution added to the flask over 45 min. Once addition is complete, the mixture is stirred for an additional 15 min before being treated with a solution of 2-naphthoyl chloride in the amount of 17.00 g (0.089 mol) dissolved in THF (25 mL) over 30 min. The mixture is warmed to -20° C. and stirred at that temperature for 18 h. After warming to 0° C., the mixture is quenched with 20% HCl (55 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCO₃ solution (2×100 mL), water (2×150 mL) and brine (150 mL), dried over MgSO₄ and filtered. The solvent is removed by rotary evaporation to give an orange/red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate dissolved in petroleum ether) to give an oil. Purity of the product is determined by thin layer chromatography and the structure confirmed by ¹ H and ¹³ C NMR.

Example 5

(±)-Linalyl(p-anisoyl)acetate

Lithium diisopropylamide in the amount of 119.0 mL (2.0 M, 0.238 mol) is placed into a 500 mL three-necked round-bottomed flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and additional funnel. The flask is cooled to -78° C. Linalyl acetate in the amount of 22.04 g (0.112 mol) is dissolved in THF (5 mL) and the resulting solution added to the flask over 45 min. Once addition is complete, the mixture is stirred for an additional 15 min before being treated with a solution of p-anisoyl chloride in the amount of 35.00 g (0.106 mol) dissolved in THF (30 mL) over 30 min. The mixture is warmed to -20° C. and stirred at that temperature for 18 h. After warming to 0° C., the mixture is quenched with 20% HCl (80 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCO₃ solution (2×100 mL), water (2×150 mL) and brine (150 mL), dried over MgSO₄ and filtered. The solvent is removed by rotary evaporation to give an orange/red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate dissolved in petroleum ether) to give an oil. Purity of the product is determined by thin layer chromatography and the structure confirmed by ¹ H and ¹³ C NMR.

Example 6

α-Terpinyl (2-naphthoyl)acetate

Lithium diisopropylamide in the amount of 171.0 mL (2.0 M, 0.342 mol) is placed into a 1000 mL three-necked round-bottomed flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. The flask is cooled to -78° C. α-Terpinyl acetate in the amount of 30.00 g (0.153 mol) is dissolved in THF (10 mL) and the resulting solution added to the flask over 45 min. Once addition is complete, the mixture is stirred for an additional 15 min before being treated with a solution of 2-naphthoyl chloride in the amount of 29.00 g (0.152 mol) dissolved in THF (50 mL) over 30 min. The mixture is warmed to -20° C. and stirred at that temperature for 18 h. After warming to 0° C., the mixture is quenched with 20% HCl (105 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with (150 mL). The combined organic layers are washed with saturated NaHCO₃ solution (2×100 mL), water (2×150 mL) and brine (150 mL), dried over MgSO₄ and filtered. The solvent is removed by rotary evaporation to give a thick semi-solid. The product mixture is purified by column chromatography (elution with 2% ethyl acetate dissolved in petroleum ether) to give a white semi-solid. Trituration with cold pentane yields the product as a white powder. Purity of the product is determined by thin layer chromatography and the structure confirmed by ¹ H and ¹³ C NMR.

Example 7

(±)-Linalyl (1-naphthoyl)acetate

Lithium diisopropylamide in the amount of 96.3 mL (2.0 M, 0.193 mol) is placed into a 500 mL three-necked round-bottom flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. The flask is cooled to -78° C. Linalyl acetate in the amount of 17.81 g (0.091 mol) is dissolved in THF (5 mL) and the resulting solution added to the flask over 45 min. Once addition is complete, the mixture is stirred for an additional 15 min before being treated with a solution of 1-naphthoyl chloride in the amount of 16.82 g (0.086 mol) dissolved in THF (25 mL) over 30 min. The mixture is warmed to -20° C. and stirred at that temperature for 18 h. After warming to 0° C., the mixture is quenched with 20% HCl (53 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCO₃ solution (2×100 mL), water (2×150 mL) and brine (150 mL), dried over MgSO₄ and filtered. The solvent is removed by rotary evaporation to give an orange/red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate dissolved in petroleum ether) to give an oil. Purity of the product is determined by thin layer chromatography and the structure confirmed by mass spectrometry, ¹ and ¹³ C NMR.

Example 8 β-γ-Hexenyl (2-naphthoyl)acetate

Lithium diisopropylamide in the amount of 133.0 mL (2.0 M, 0.266 mol) is placed into a 500 mL three-necked round-bottomed flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and additional funnel. The flask is cooled is -78° C. β-γ-Hexenyl acetate in the amount of 17.80 g (0.125 mol) is dissolved in THF (10 mL) and the resulting solution added to the flask over 45 min. Once addition is complete, the mixture is stirred for an additional 15 min before treated with a solution of 2-naphthoyl chloride in the amount of 22.51 g (0.118 mol) dissolved in THF (30 mL) over 30 min. The mixture is warmed to -20° C. and stirred at that temperature for 18 h. After warming to 0° C., the mixture is quenched with 20% HCl (70 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCO₃ solution (2×100 mL), water (2×150 mL) and brine (150 mL), dried over MgSO₄ and filtered. The solvent is removed by rotary evaporation to give an orange/red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate dissolved in petroleum ether) to give an oil. Purity of the product is determined by thin layer chromatography and the structure confirmed by ¹ H and ¹³ C. NMR.

Example 9

9-Decen-1-yl (2-naphthoyl)acetate

Lithium diisopropylamide in the amount of 79.8 mL (2.0 M, 0.160 mol) is placed into a 250 mL three-necked round-bottomed flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. The flask is cooled to -78° C. Roseate acetate in the amount of 14.91 g (0.075 mol) is dissolved in THF (5 mL) and the resulting solution added to the flask over 45 min. Once addition is complete, the mixture is stirred for an additional 15 min before being treated with a solution of 2-naphthoyl chloride in the amount of 13.80 g (0.071 mol) dissolved in THF (25 mL) over 30 min. The mixture is warmed to -20° C. and stirred at that temperature for 18 h. After warming to 0° C., the mixture is quenched with 20% HCl (47 mL). The mixture is poured into a separatory funnel containing ether (125 mL) and water (225 mL). The aqueous layer is extracted with ether (125 mL). The combined organic layers are washed with saturated NaHCO₃ solution (3×95 mL), water (2×150 mL) and brine (150 mL), dried with MgSO₄ and filtered. The solvent is removed by rotary evaporation to give an orange/red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate dissolved in hexane) to give an oil. Purity of the product is determined by thin layer chromatography and the structure confirmed by ¹ H and ¹³ C NMR.

Example 10

Linalyl (nonanoyl)acetate

Lithium diisopropylamide in the amount of 133.7 mL (2.0 M, 0.267 mol) is placed into a 500 mL three-necked round-bottomed flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. The flask is cooled -78° C. Linalyl acetate in the amount of 24.73 g (0.126 mol) is dissolved in THF (40 mL) and the resulting solution added to the flask over 45 min. Once addition is complete, the mixture is stirred for an additional 15 min before being treated with a solution of nonanoyl chloride in the amount of 21.88 g (0.119 mol) over 30 min. The mixture is warmed to -20° C. and stirred at that temperature for 18 h. After warming to 0° C., the mixture is quenched with 20% HCl (60 mL). The mixture is poured into a separatory funnel containing ether (160 mL) and water (275 mL). The aqueous layer is extracted with ether (160 mL). The combined organic layers are washed with saturated NaHCO₃ solution (2×100 mL), water (2×150 mL) and brine (150 mL), dried over MgSO₄ and filtered. The solvent is removed by rotary evaporation to give an orange/red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate dissolved in hexane) to give an oil. Purity of the product is determined by thin layer chromatography and the structure confirmed by ¹ H and ¹³ C NMR.

Example 11

Dihyromyrencyl (nonanoyl)acetate

Lithium diisopropylamide in the amount of 75.7 mL (2.0 M, 0.151 mol) is placed into a 500 mL three-necked round flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition funnel. The flask is cooled to -78° C. Dihydromyrcenyl acetate in the amount of 14.14 g (0.071 mol) is dissolved in THF (20 mL) and the resulting solution added to the flask over 45 min. Once addition is complete, the mixture is stirred for an additional 15 min before being treated with a solution of nonanoyl chloride in the amount of 12.38 g (0.067 mol) over 30 min. The mixture is warmed to -20° C. and stirred at that temperature for 18 h. After warming to 0° C., the mixture is quenched with 20HCl (55 mL). The mixture is poured into a separatory funnel containing ether (150 mL) and water (275 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCO₃ solution (2×100 mL), water (2×150 mL) and brine (150 mL), dried over MgSO₄ and filtered. The solvent is removed by rotary evaporation to give an orange/red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate dissolved in hexane) to give an oil. Purity of the product is determined by thin layer chromatography and the structure confirmed by ¹ H and ¹³ C NMR.

Examples of Dryer Sheet Composition Containing β-Ketoesters

    __________________________________________________________________________     Formulation Example                                                                      A   B   C   D   E   F   G   H                                          Ingredient Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Wt. %                   __________________________________________________________________________     DEQA (1)  44.23                                                                              39.16                                                                              --  --  --  --  --  --                                         DEQA (2) -- -- 51.81 21.81 -- 34.74 -- --                                      DEQA (3) -- -- -- -- 28.32 -- -- --                                            DEQA (4) -- -- -- -- -- -- 31.33 --                                            DTDMAMS (5) -- -- -- -- -- -- -- 18.64                                         Cosoftener (6) 49.60 34.41 26.38 21.33 39.41 23.20  28.04                      Glycosperse S-20 (7) -- -- 15.38 12.38 -- 18.04 -- --                          Sorbitan Monooleate -- -- -- -- 25.75 -- -- --                                 Glycerol Monostearate -- -- -- -- -- 18.04 -- 18.87                            Clay  4.02  4.02  3.16  3.16  4.12  4.02  4.52  3.91                           Perfume  1.55  0.80  1.75  0.70  1.15 --  1.11 --                              Perfume/Cyclodextrin -- -- -- -- -- -- 18.38 --                                complex                                                                        Product of Example 1 --  2.50 -- --  1.25 --  0.25 --                          (8)                                                                            Product of Example 9  0.60 -- -- -- -- -- --  2.60                             (9)                                                                            Product of Example 10 -- --  1.52 -- --  1.96 -- --                            (10)                                                                           Product of Example 11 -- -- --  2.60 -- -- -- --                               (11)                                                                           Polyamine (12) --  2.10 --  4.10 -- -- --  5.20                                Stearic Acid -- 55.78 -- 33.92 -- -- -- 22.74                                __________________________________________________________________________      (1) Di(oleyloxyethyl) dimethyl ammonium methylsulfate                          (2) Di(soft-tallowyloxyethyl)hydroxyethyl methyl ammonium methylsulfate        (3) Di(soft-tallowyloxyethyl)dimethyl ammonium methylsulfate                   (4) Di(soft-tallowyloxy)trimethyl ammoniopropane methylsulfate                 (5) Ditallow dimethyl ammonium methylsulfate                                   (6) 1:2 Ratio of stearyl dimethyl ammine:triplepressed stearic acid            (7) Polyethoxylated sorbitan monostearate, available from Lonza                (8) (±)Linalyl (2naphthoyl)acetate                                          (9) 9Decen-1-yl(2-naphthoyl)acetate                                            (10) (±)Linalyl (nonanoyl)acetate                                           (11) Dihydromyrcenyl (nonanoyl)acetate                                         (12) Ethoxylated Poly(ethyleneimine)MW 1800                              

Preparation of Coating Mix (Formula A)

A batch of approximately 200 g is prepared as follows: Approximately 99.2 g of co-softener and about 88.5 DEQA(1) are melted separately at about 80° C. They are combined with high shear mixing in a vessel immersed in a hot water bath to maintain the temperature between 70-80° C. Calcium bentonite clay (8 g) is mixed to achieve the desired viscosity. The Product of Example 9 (1.2 g) and perfume (3.1 g) are added to the formula and mixed until homogeneous.

Coating mixes for Formulas B-H are made in a like manner, using the materials indicated in the table above.

Preparation of Fabric Conditioning Sheets

The coating mixture is applied to pre-weighted substrate sheets of about 6.75 inches×12 inches (approximately 17 cm×30 cm) dimensions. The substrate sheets are comprised of about 4-denier spun bonded polyester. A small amount of the formula is placed on a heated metal plate with a spatula and then is spread evenly with a wire metal rod. A substrate sheet is placed on the metal place to absorb the coating mixture. The sheet is then removed from the heated metal plate and allowed to cool to room temperature so that the coating mix can solidify. The sheet is weighted to determine the amount of coating mixture on the sheet. The target sheet weight is 3.5 g. If the weight is in excess of the target weight, the sheet is placed back on the heated metal plate to remelt the coating mixture and remove some of the excess. If the weight is under the target weight, the sheet is also placed on the heated metal plate and more coating mixture is added. 

What is claimed is:
 1. A dryer activated fabric softening composition comprising:a) from 0.01% to 15% by weight, of a β-ketoester selected from the group consisting of 3,7-dimethyl-1,6-octadien-3-yl-3-(β-naphthyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(4-methoxyphenyl)-3-oxo-propionate,2,6-dimethyl-7-octen-2-yl 3-(4-nitrophenyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(β-naphthyl)-3-oxo-propionate, 3,7-dimethyl-1,6-octadien-3-yl 3-(4-methoxyphenyl)-3-oxo-propionate, (α,α-4-trimethyl-3-cyclohexenyl)methyl 3-(β-naphthyl)-3-oxo-propionate, 3,7-dimethyl-1,6-octadien-3-yl 3-(α-naphthyl)-3-oxo-propionate, cis 3-hexen-1-yl 3-(β-naphthyl)-3-oxo-propionate, 9-decen-1-yl 3-(β-naphthyl)-3-oxo-propionate, 3,7-dimethyl-1,6-octadien-3-yl 3-(nonanyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(nonanyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-oxo-butyrate, 3,7-dimethyl-1,6-octadien-3-yl 3-oxo-butyrate, 2,6-dimethyl-7-octen-2-yl 3-(β-naphthyl)-3-oxo-2-methylpropionate, 3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-2,2-dimethylpropionate, 3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-2-methylpropionate, 3,7-dimethyl-2,6-octadienyl 3-(β-naphthyl)-3-oxo-propionate, 3,7-dimethyl-2,6-octadienyl 3-heptyl-3-oxo-propionate, and mixtures thereof; b) from 10% to 99.99% by weight, of a fabric softening compound; c) optionally, the balance carriers and other adjunct ingredients.
 2. A composition according to claim 1 wherein said β-ketoester is 3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-propionate.
 3. A composition according to claim 1 wherein said β-ketoester comprises an R unit derived from an alcohol selected from the group consisting of 3,7-dimethyl-1,6-octadien-3-ol, 2,6-dimethyl-7-octen-2-ol, (α,α-4-trimethyl-3-cyclohexenyl)methanol, cis 3-hexen-1-ol, 9-decen-1-ol, and mixtures thereof.
 4. A dryer activated fabric conditioning composition comprising:a) from 0.01% to 15% by weight, of a β-ketoester selected from the group consisting of 3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3)-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(4-methoxyphenyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(4-nitrophenyl)-3-oxo-propione, 2,6-dimethyl-7-octen-2-yl 3-(β-naphthyl)-3-oxo-propionate, 3,7-dimethyl-1,6-octadien-3-yl 3-(4-methoxyphenyl)-3-oxo-propionate, (α,α-4-trimethyl-3-cyclohexenyl)methyl 3-(β-naphthyl)-3-oxo-proprionate, 3,7-dimethyl-1,6-octadien-3-yl 3-(α-naphthyl)-3-oxo-priopionate, cis 3-hexen-1-yl 3-(β-naphthyl)-3-oxo-propionate, 9-decen-1-yl 3-(β-naphthyl)-3-oxo-proprionate, 3,7-dimethyl-1,6-octadien-3-yl 3-(nonanyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(nonanyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-oxo-butyrate, 3,7-dimethyl-1,6-octadien-3-yl 3-oxo-butyrate, 2,6-dimethyl-7-octen-2-yl 3-(β-naphthyl)-3-oxo-2-methylpropionate, 3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-2,2-dimethylpropionate, 3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-2-methylpropionate, 3,7-dimethyl-2,6-octadienyl 3-(β-naphthyl)-3-oxo-propionate, 3,7-dimethyl-2,6-octadienyl 3-heptyl-3-oxo-propionate, and mixtures thereof; b) from 10% to 95% by weight, of a quaternary ammonium compound softener selected from the group consisting of compounds having the formula: ##STR31## wherein each Y is --O--(O)C--, or --C(O)--O--, each R¹ is C₁ -C₆ alkyl; each R² is C₈ -C₃₀ hydrocarbyl or substituted hydrocarbyl; p is 1 to 3; each v is an integer from 1 to 4; X is a softener-compatible amion; ##STR32## wherein each Q is --O--(O)C--, or --C(O)--O; each R¹ is C₁ -C₄ alkyl, C₁ -C₄ hydroxylalkyl; each R² is C₈ -C₃₀ hydrocarbyl or substituted hydrocarbyl; each v is an integer from 1 to 4; X is a softener-compatible anion; ##STR33## R¹ is C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl; each R² is C₈ -C₃₀ hydrocarbyl or substituted hydrocarbyl; R⁴ is C₁ -C₄ hydroxyalkyl; each v is an integer from 1 to 4; X is a softener-compatible anion; ##STR34## wherein each Y" has the formula: ##STR35## and mixtures thereof; each R¹ is C₁ -C₆ alkyl; each R² is C₈ -C₃₀ hydrocarbyl or substituted hydrocarbyl; p is 1 to 3; each v is an integer from 1 to 4; X is a softener-compatible anion; and mixtures thereof; c) optionally, from 0% to 95% by weight, of a co-softener comprising a carboxylic acid salt of a tertiary amine, tertiary amine ester, and mixtures thereof; d) optionally, from 0% to 50% by weight, of a nonionic softener; and e) an ingredient selected from the group consisting of colorants, preservatives, optical brighteners, opacifiers, anti-shrinkage agents, anti-wrinkle agents, fabric crisping agents, spotting agents, germicides, fungicides, anti-corrosion agents, antifoam agents, and mixtures thereof;provided the iodine value of the fatty acyl units which comprise the softeners of (b), (c), and (d) is from 3 to
 60. 5. A composition according to claim 4 wherein said fabric softener is selected from the group consisting of N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate, N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate, N,N-di(tallowylamidoethyl)-N-methyl, N-(2)-hydroxyethyl) ammonium methyl sulfate, N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride, N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride, N,N-di(2-tallowyloxyethyl-carbonyloxyethyl)-N,N-dimethyl ammonium chloride, N,N-di(2-canolyloxyethyl-carbonyloxyethyl)-N,N-dimethyl ammonium chloride, N-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride, N-(2-canolyloxy-2-ethyl)-N-2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride, and mixtures thereof.
 6. A composition according to claim 4 wherein said β-kotoester is 3,7-dimethyl-1,6-octadien-3-yl 3-(62-naphthyl)-3-oxo-propionate.
 7. A composition according to claim 4 further comprising from about 0.1% to about 5% by weight, of a soil release polymer.
 8. A composition according to claim 4 further comprising from about 0.5% to about 60% by weight, of a cyclodextrin/perfume inclusion complex.
 9. A composition according to claim 4 further comprising from about 0.01% to about 0.2% by weight, of a stabilizer selected from the group consisting of ascorbic acid, ascorbic palmitate, propyl gallate, ter-butylhyfroquinone, butylated hydroxytoluene, butylated hydroxyanisole, and mixtures thereof.
 10. An article of manufacture comprising:A) a flexible substrate; and B) a composition comprising:a) from 0.1% to 15% by weight, of a β-ketoester selected from the group consisting of 3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(4-methoxyphenyl)-3-oxo-proprionate, 2,6-dimethyl-7-octen-2-yl 3-(4-nitrophenyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(β-naphthyl)-3-oxo-propionate, 3,7-dimethyl-1,6-octadien-3-yl 3-(4-methoxyphenyl)-3-oxo-propionate, (α,α-4-trimethyl-3-cyclohexenyl)methyl 3-(βnaphthyl)-3-oxo-propionate, 3,7-dimethyl-1,6-octadien-3-yl 3-(αnaphthyl)-3-oxo-propionate, cis 3-hexen-1-yl 3-(β-naphthyl)-3-oxo-propionate, 9-decen-1-yl 3-(β-naphthyl)-3-oxo-propionate, 3,7-dimethyl-1,6-octadien-3-yl 3(nonanyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(nonanyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-oxo-butyrate, 3,7-dimethyl-1,6-octadien-3-yl 3-oxo-butyrate, 2,6-dimethyl-7-octen-2-yl 3-(β-naphthyl)-3-oxo-2-methylpropionate, 3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-2,2-dimethylpropionate, 3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-2-methylpropionate, 3,7-dimethyl-2,6-octadienyl 3-(β-naphthyl)-3-oxo-proprionate, 3,7-dimethyl-2,6-octadienyl 3-heptyl-3-oxo-propionate, and mixtures thereof; b) from 10% to 95% by weight, of a quaternary ammonium compound softener selected from the group consisting of compounds having the formula: ##STR36## wherein each Y is --O--(O)C--, or --C(O)--O; each R¹ is C₁ -C₆ alkyl; each R² is C₈ -C₃₀ hydrocarbyl or substituted hydrocarbyl; p is 1 to 3; each v is an integer from 1 to 4; X is a softener-compatible anion; ##STR37## wherein each Q is --O--(O)C--, or --C(O)--O; each R¹ is C₁ -C₄ alkyl, C₁ -C₄ hydroxyalkyl; each R² is C₈ -C₃₀ hydrocarboyl or substituted hydrocarbyl; each v is an integer from 1 to 4; X is a softener-compatible anion; ##STR38## R¹ is C₁ -C₄ alkyl, C₁ -C₃₀ hydrocarbyl or substituted hydrocarbyl; R⁴ is C₁ -C₄ hydroxyalkly; each v is an integer from 1 to 4; X is a softener-compatible anion; ##STR39## wherein each Y" has the formula: ##STR40## and mixtures thereof; each R¹ is C₁ -C₆ alkyl; each R² is C₈ -C₃₀ hydrocarbyl or substituted hydrocarbyl; p is 1 to 3; each v is an integer from 1 to 4; X is a softener-compatible anion; and mixtures thereof; c) optionally, from 0% to 95% by weight, of a co-softener comprising a carboxylic acid salt of a tertiary amine, tertiary amine ester, and mixtures thereof; d) optionally, from 0% to 50% by weight, of a nonionic softener; and e) an ingredient selected from the group consisting of colorants, preservatives, optical brighteners, opacifiers, anti-shrinkage agents, anti-wrinkle agents, fabric crisping agents, spotting agents, germicides, fungicides, anti-corrosion agents, antifoam agents, and mixtures thereof;provided the iodine value of the fatty acyl units which comprise the softeners of (b), (c), and (d) is from 3 to
 60. 11. An article of manufacture according to claim 10 wherein said fabric softener is selected from the group consisting of N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate, N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate, N,N-di(tallowylamidoethyl)-N-methyl, N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate, N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride, N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride, N,N-di(2-tallowyloxyethyl-carbonyloxyethyl)-N,N-dimethyl ammonium chloride, N,N-di(2-canolyloxyethyl-carbonyloxyethyl)-N,N-dimethyl ammonium chloride, N-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride, N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride, and mixtures thereof.
 12. An article of manufacture according to claim 10 wherein said β-ketoester is 3,7-dimethyl-1,6-octadien-3-yl 3-(β-naphthyl)-3-oxo-propionate. 